Organic field-effect transistors based on Langmuir–Blodgett films of substituted phthalocyanines

Three substituted phthalocyanines (Pcs), two asymmetrical and one symmetrical, named amino-tri-tert-butyl-phthalocyanine (AmBuPc), 1,8-naphthalimide-tri-tert-butyl-phthalocyanine (NaBuPc), and tetra-iso-propoxy-phthalocyaninato copper(II) (i-Pro-CuPc), were used as semiconductor layers in organic field-effect transistors (OFETs) based on their Langmuir–Blodgett (LB) films. These substituted Pcs possess good solubility in common organic solvents. From the long-wavelength absorption edge of their UV–VIS absorption spectra and their electrochemical data, the highest occupied molecular orbital and the lowest unoccupied molecular orbital were determined and the energy band diagram of their OFETs was deduced. The narrower energy gaps of them indicated stronger electron donor–acceptor ability than other symmetrical Pcs because of the substituents at the peripheral ring. The results of their OFETs demonstrated that the LB films of these substituted Pcs can be used as semiconducting layers of OFETs functioned as p-channel accumulation devices. From the electrical characteristics of their OFETs, the channel carrier mobilities of AmBuPc, NaBuPc and i-Pro-CuPc were calculated to be about 2.84×10⁻⁵, 4.42×10⁻⁴ and 3.25×10⁻⁴ cm² V⁻¹ s⁻¹, respectively.     

Simultaneous determination of lead and cadmium at a glassy carbon electrode modified with Langmuir–Blodgett film of p-tert-butylthiacalix[4]arene

A glassy carbon electrode (GCE) modified with a Langmuir–Blodgett (LB) film of p-tert-butylthiacalix[4]arene (TCA) has been investigated as a disposable sensor for measuring the trace levels of lead and cadmium. The possibility of determining lead and cadmium at trace levels was examined with differential pulse stripping voltammetry in the measurement step. The electrochemical response was characterized with respect to supporting electrolyte, pH of solution, accumulation time, accumulation potential, layers of the LB films, and possible interferences. Calibration plots were found to be linear in the range 2 × 10⁻⁷ to 5 × 10⁻⁵ mol l⁻¹ (Cd²⁺) and 1 × 10⁻⁷ to 2.5 × 10⁻⁵ mol l⁻¹ (Pb²⁺); the detection limits were 2 × 10⁻⁸ mol l⁻¹ (Cd²⁺) and 8 × 10⁻⁹ mol l⁻¹ (Pb²⁺). Possible recognition mechanism was also discussed. From the analysis of real samples (river, lake and tap water) it can be concluded that the method is sensitive and reproducible in determining of these elements and can be used in the analysis of natural water samples.     

Interaction of Langmuir–Blodgett and spin-coated films of μ-carbido-bridged ironphthalocyanine with NO2: Optical and conductimetric behaviour

The present study investigates the interaction of NO₂ gas and μ-carbido-bridged iron phthalocyanine (PcFeCFePc) films obtained by Langmuir–Blodgett (LB) and spin-coating (SC) techniques. The phthalocyanine bridged dimer under study belongs to the polynuclear unsubstituted phthalocyanines class and presents poor solubility: in contrast the corresponding N-base bis-adducts are soluble enough in organic solvents to be deposited by Langmuir–Blodgett and spin-coating techniques. The reaction with NO₂ is monitored by visible spectra variation that shows identical behaviour for both kinds of films, indicating that the chemical reaction between the gas and the films is independent of the deposition method. The electrical conductivity change as a function of time with NO₂ is instead dissimilar: for spin-coated films it shows a behaviour already observed for sandwich-type phthalocyanine whereas for LB films it resembles that of monomeric phthalocyanine. Such a response implies that the charges (holes) generated in the oxidation/reduction process are carried differently through the material, and we attempt to explain this behaviour taking into account the two different structural and morphological features induced by the two techniques.     

The influence of the surface morphologies of Langmuir Blodgett (LB) thin films of porphyrins on their gas sensing properties

In this work, 2,3,7,8,12,13,17,18-Octaethyl-21H,23H-porphine (OEP) in its free base form and metalated with iron (III) chloride (FeOEP), magnesium(II) (MgOEP) and cobalt(II) (CoOEP) have been used to fabricate Langmuir-Blodgett (LB) thin films. Using the surface pressure-surface area (Π-A) isotherm graphs optimum conditions for thin film deposition have been determined and by changing the deposition parameters various thin films have been deposited. Quartz Crystal Microbalance (QCM) system was used to investigate their gas sensing performances during exposure to Volatile Organic Compounds (VOCs) including chloroform, benzene and toluene. The surface properties have been investigated using Atomic Force Microscopy (AFM) and analyzed together with the QCM results to understand the effect of the surface properties on gas sensing mechanism. It is observed that larger surface area leads to higher response in gas sensing applications in terms of resonance frequency change.     

Effect of annealing and temperature on the NO2 sensing properties of tellurium based films

Influences of temperature and annealing on the electrical and sensing properties toward NO₂ of tellurium based films were investigated. The annealing at temperatures more than 100 °C causes a sharp decrease both of electrical resistance and sensitivity of the films. SEM analyzes indicated that annealing induced structural evolution of the films, including growth of large crystals in the matrix. Temperature-dependent electrical conductivity is strongly affected by presence of an NO₂ environment. The sensitivity toward NO₂, being controlled by gas concentration, decreases with operating temperature increase. On the other hand, the increase of operating temperature leads to a reduction of response–recovery times.

The results are discussed taking into consideration the contributions of grain boundary as well as grain bulk and surface resistance to the total conductivity. It is assumed the surface, including grain boundary, hole-enriched region is formed as a result of dangling bond chalcogen’s lone-pair electron interaction. Chemisorption of NO₂ molecules is accompanied by hole enrichment of the surface and grain boundary region, due to interaction of these molecules with lone-pair electrons.     

Pyroelectric and dielectric properties of sol–gel derived barium–strontium–titanate (Ba0.64Sr0.36TiO3) thin films

The barium–strontium–titanate (BST, Ba_0.64Sr_0.36TiO₃) thin films have been prepared by the sol–gel method on a platinum-coated silicon substrate. The resulting thin films show very good dielectric and pyroelectric properties. The dielectric constant and dissipation factor for Ba_0.64Sr_0.36TiO₃ thin film at a frequency of 200 Hz were 592 and 0.028, respectively. The dependence of the capacitance as a function of the voltage shows a strongly non-linear character, and two peaks characterizing spontaneous polarization switching can be clearly seen in this curve, indicating that the films have a ferroelectric nature. The capacitance changed from 495 to 1108 pF with the applied voltage in the −5 to +5 V range at a frequency of 100 kHz. The peak pyroelectric coefficient at 30 °C is 1080 μC/m² K. The pyroelectric coefficient at room temperature (25 °C) is 1860 μC/m² K, and the figure-of-merit of this film is 37.4 μC/m³ K. The high pyroelectric coefficients and the greater figures-of-merit of Ba_0.64Sr_0.36TiO₃ thin films make it possible to be used for thermal infrared detection and imaging.     

Gas sensors for air quality monitoring: realisation and characterisation of undoped and noble metal-doped SnO2 thin sensing films deposited by the pulsed laser ablation

Undoped and noble metal-doped very thin SnO₂ sensing layers deposited by the pulsed laser ablation (PLA) technique upon micromachined Si substrate heater elements have been extensively characterised. The main objective behind the effort carried out in this work has been the challenging perspective to define a sensing layer technology and a sensor operating mode (continuous (DC) vs. pulsed temperature (PT) mode) which allows the long term measuring and the easy discrimination of very low concentration of benzene by an interfering species like carbon monoxide, both present in the outdoor air. The experimental results reported in this work have shown that combining the sensor technology with a suitable catalytic element (in the present case, gold) and a proper sensor operating mode, very low concentration of benzene can be revealed with a sufficient selectivity towards CO. One of the major problems encountered during the long term test of the sensors has been the loss of the sensitivity to benzene with the time. An attempt has been made to explain the reason of this experimental result. We firmly believe that many factors contribute to it. Among them, the annealing of point defects associated with the oxygen vacancies as well as the loss of the catalytic efficiency by the added Au layer as effect of a possible coalescence of the metal clusters at the sensor working temperature (T400°C). To partially reduce the cluster mobility and to preserve the benzene sensitivity, the last assumption would suggest to operate the sensors, no matter if in DC or in PT mode, at a temperature lower than that used in this work.     

A comparative study of the physical properties of CdS, Bi2S3 and composite CdS–Bi2S3 thin films for photosensor application

Thin films of CdS, Bi₂S₃ and composite CdS–Bi₂S₃ have been deposited using modified chemical bath deposition (M-CBD) technique. The various preparative parameters were optimized to obtain good quality thin films. The as-deposited films of CdS, Bi₂S₃ and composite were annealed in Ar gas at 573 K for 1 h. A comparative study was made for as-deposited and annealed CdS, Bi₂S₃ and composite thin films. Annealing showed no change in crystal structure of these as-deposited films. However, an enhancement in grain size was observed by AFM studies. In addition change in band gap with annealing was seen. A study of spectral response, photosensitivity showed that the films can be used as a photosensor.